NZ623683B2 - Non-aqueous liquid concentrate for aqueous dispersion - Google Patents
Non-aqueous liquid concentrate for aqueous dispersion Download PDFInfo
- Publication number
- NZ623683B2 NZ623683B2 NZ623683A NZ62368312A NZ623683B2 NZ 623683 B2 NZ623683 B2 NZ 623683B2 NZ 623683 A NZ623683 A NZ 623683A NZ 62368312 A NZ62368312 A NZ 62368312A NZ 623683 B2 NZ623683 B2 NZ 623683B2
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- New Zealand
- Prior art keywords
- liquid concentrate
- aqueous liquid
- aqueous
- aqueous dispersion
- dispersion
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 90
- 235000014666 liquid concentrate Nutrition 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920001519 homopolymer Polymers 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 239000011780 sodium chloride Substances 0.000 claims abstract description 38
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 33
- 239000008158 vegetable oil Substances 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002472 Starch Polymers 0.000 claims abstract description 22
- 239000004927 clay Substances 0.000 claims abstract description 22
- 229910052570 clay Inorganic materials 0.000 claims abstract description 22
- 235000019698 starch Nutrition 0.000 claims abstract description 22
- 239000008107 starch Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003549 soybean oil Substances 0.000 claims description 15
- 235000012424 soybean oil Nutrition 0.000 claims description 15
- 235000012343 cottonseed oil Nutrition 0.000 claims description 14
- 239000002385 cottonseed oil Substances 0.000 claims description 13
- 230000001264 neutralization Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003002 pH adjusting agent Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 229910000271 hectorite Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M Sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims 1
- -1 Carboxyvinyl Chemical group 0.000 abstract description 5
- 229920000058 polyacrylate Polymers 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 33
- 235000008504 concentrate Nutrition 0.000 description 22
- 239000012141 concentrate Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 231100000078 corrosive Toxicity 0.000 description 4
- 231100001010 corrosive Toxicity 0.000 description 4
- 238000007706 flame test Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 210000001772 Blood Platelets Anatomy 0.000 description 3
- 206010042602 Supraventricular extrasystoles Diseases 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000875 corresponding Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001888 polyacrylic acid Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229940092782 Bentonite Drugs 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 102000014961 Protein Precursors Human genes 0.000 description 2
- 108010078762 Protein Precursors Proteins 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical compound [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 2
- 235000010599 Verbascum thapsus Nutrition 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000828 canola oil Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- KARVSHNNUWMXFO-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane;hydrate Chemical compound O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O KARVSHNNUWMXFO-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229960001631 Carbomer Drugs 0.000 description 1
- 240000007842 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229940080314 Sodium Bentonite Drugs 0.000 description 1
- 240000001016 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 240000008529 Triticum aestivum Species 0.000 description 1
- 241000209149 Zea Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000005824 corn Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000000994 depressed Effects 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- TUKQLEWOUPCTOS-UHFFFAOYSA-N dimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane;hydrate Chemical compound O.[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O TUKQLEWOUPCTOS-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002459 sustained Effects 0.000 description 1
- 230000002195 synergetic Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000021307 wheat Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
Abstract
non-aqueous liquid concentrate comprising starch, an acrylic acid homopolymer salt, vegetable oil, and clay. The non-aqueous liquid concentrate forms an aqueous dispersion when added to water and is capable of clinging to a surface. Also disclosed are methods of forming the an aqueous dispersion by adding the non-aqueous liquid concentrate to water and methods of applying the aqueous dispersion to a substrate to suppress a fire. In particular embodiments the acrylic acid homopolymer salt is: Carboxyvinyl homopolymer salt, polyacrylate homopolymer salt or 2 propenoic homopolymer salt y adding the non-aqueous liquid concentrate to water and methods of applying the aqueous dispersion to a substrate to suppress a fire. In particular embodiments the acrylic acid homopolymer salt is: Carboxyvinyl homopolymer salt, polyacrylate homopolymer salt or 2 propenoic homopolymer salt
Description
NON-AQUEOUS LIQUID CONCENTRATE FOR AQUEOUS DISPERSION
BACKGROUND
Aqueous dispersions are generally known in industry to be useful for a number of
applications. These ations include use as a carrier for active ingredients or for
coating substrates. The physical properties of the aqueous dispersion dictate the useful
applications of the aqueous dispersion.
Recently aqueous dispersions have been utilized to suppress fire. Aqueous dispersions
that are currently utilized to suppress fire can be difficult to formulate and may not exhibit
ity. In addition some of these s dispersions or precursors thereof can be
corrosive or have a pH that is not neutral. Many of these aqueous dispersions require a pH
modifier such strong alkalis such as ides or amines, in order to achieve a ning
effect in aqueous dispersions needed to coat a substrate. In addition, a problem to
overcome for chemical retardant formulations and aqueous dispersions in general, is the
environmental impact of these formulations. Environmentally friendly and pH neutral
formulations are desired.
BRIEF Y
The present disclosure relates to non-aqueous liquid concentrates. In particular the t
disclosure relates to a non-aqueous liquid concentrate that may have shear thinning
properties and that when added to water forms a dispersion having shear ng
properties. The dispersion can be pH neutral and cling to a surface and be useful for any
number of applications.
In one rative embodiment, a non-aqueous liquid concentrate includes starch, an
acrylic acid homopolymer salt, vegetable oil, and clay. The non-aqueous liquid
concentrate forms an aqueous dispersion when added to water and the aqueous dispersion
is capable of clinging to a surface.
In another illustrative embodiment, an aqueous dispersion includes water and the non
aqueous liquid concentrate that includes starch, an c acid homopolymer salt, a
vegetable oil and clay. The aqueous dispersion has a neutral pH, is shear thinning and
thixotropic.
A further illustrative embodiment is a method that includes diluting the non-aqueous
liquid concentrate with water to form the aqueous dispersion and ing the aqueous
dispersion onto a substrate and the aqueous dispersion clings to the substrate. In some
embodiments the aqueous sion suppresses a fire.
These and various other features and advantages will be apparent from a reading of the
following detailed description.
DETAILED DESCRIPTION
In the following description, it is to be understood that other embodiments are
contemplated and may be made without departing from the scope or spirit of the t
disclosure. The following detailed description, therefore, is not to be taken in a ng
sense.
All ific and cal terms used herein have meanings commonly used in the art
unless otherwise specified. The definitions provided herein are to facilitate understanding
of certain terms used frequently herein and are not meant to limit the scope of the present
disclosure. Wt% is weight percent and is based on the total weight of the concentrate or
aqueous dispersion.
Unless otherwise indicated, all s expressing feature sizes, amounts, and physical
properties used in the specification and claims are to be understood as being modified in
all instances by the term "about." Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the foregoing ication and attached claims are
imations that can vary depending upon the desired properties sought to be ed
by those skilled in the art utilizing the teachings disclosed herein.
As used in this specification and the appended claims, the singular forms "a", "an", and
"the" encompass embodiments having plural referents, unless the content clearly dictates
otherwise. As used in this specification and the appended claims, the term "or" is
generally employed in its sense including "and/or" unless the content clearly dictates
otherwise.
As used herein, "have", "having", "include", "including", "comprise", "comprising" or the
like are used in their open ended sense, and generally mean "including, but not d to."
It will be understood that the terms "consisting of and "consisting essentially of are
ed in the term "comprising," and the like.
The term "acrylic acid homopolymer salt" refers to a carboxyvinyl homopolymer salt, or a
polyacrylate homopolymer salt, or a 2-propenoic acid homopolymer salt. The salt can be
any useful salt such as , or potassium.
The present disclosure relates to non-aqueous liquid concentrates. In particular the present
disclosure relates to a non-aqueous liquid concentrate that when added to water forms a
sion having shear ng properties. The dispersion can be pH neutral and cling to
a surface and be useful for any number of applications. In some embodiments, the pH
neutral aqueous dispersion can cling to a surface and suppress or extinguish a fire. The
non-aqueous liquid concentrates can have a neutral pH and in many embodiments do not
include pH modifiers such as strong alkalis such as hydroxides or amines, in order to
achieve a thickening effect in aqueous dispersions (formed from the non-aqueous liquid
concentrates) needed to coat a substrate. The aqueous dispersion is a dilution of a non
aqueous liquid concentrate and water. The non-aqueous liquid concentrate includes
starch, an acrylic acid homopolymer salt, vegetable oil and clay. A synergistic
relationship at particular wt% ranges of starch, an acrylic acid homopolymer salt,
vegetable oil and clay has been discovered. The non-aqueous liquid trate can be
utilized to form an aqueous dispersion that is used in any coating application where a shear
thinning s dispersion having a neutral pH that is non-caustic in either s
dispersion or non-aqueous liquid concentrate forms is useful, or desired. While the
t disclosure is not so limited, an appreciation of various s of the disclosure
will be gained through a discussion of the examples provided below.
In many embodiments, when diluted or dispersed into water or injected into a stream of
water, the non-aqueous liquid concentrate can make up from 0.1 to 10 wt% or from 0.1 to
wt% of the aqueous dispersion. In some embodiments, when diluted or dispersed into
water or injected into a stream of water, the non-aqueous liquid trate can make up
from 0.5 to 3 wt% of the aqueous dispersion.
The aqueous dispersion formed by ng the non-aqueous liquid concentrate with water
can be pumped or sprayed by typical high pressure pumping equipment or by low-pressure
individual tanks. The aqueous dispersion can have a "high yield value" (the force that
must be applied to a fluid layer before any movement is produced), meaning it has an
initial resistance to flow under stress but then is shear thinning, and when used, ts
"cling," meaning it has the ability at rest, to return to a pseudo-plastic or thixotropic gel.
The aqueous dispersion does not readily separate or settle and can be easily sprayed and
thickens when it contacts a wall or ceiling e, or any other surface. In ghting
application, for example, this gives the firefighter the y, unlike water alone, to build
thickness and hold the dispersion or aqueous gel on vertical or overhead surfaces. While
not wishing to be bound to any ular theory, it is believed that both the aqueous
dispersion's mass and the cling properties (cohesive and adhesive th) allow it to act
as a heat sink. This clinging to the es causes the overall temperature of the surfaces
to generally remain at or below the boiling point of water. The heat sink effect can
maintain the temperature of the surface coated with the dispersion or aqueous gel at about
100 degree centigrade or lower until the water in the s dispersion has been
evaporated.
The starch, acrylic acid homopolymer salt, clay and vegetable oil can be mixed or blended
utilizing a mixer, and the like, to obtain a homogenous and non-aqueous liquid concentrate
composition. It has been found that these non-aqueous liquid concentrate compositions
quickly form stable gels, aqueous suspensions or aqueous dispersions when combined
with water. In many embodiments, the dilute dispersion or aqueous gel or suspension has
a pH in the range of 6.5 to 7.5 and the aqueous gel or dilute dispersion or sion
clings to a surface positioned at nearly any orientation. The aqueous gel or dilute
dispersion or sion may form a protective char layer upon heating or fire contact.
In many embodiments the non-aqueous liquid concentrate es starch, an acrylic acid
homopolymer salt, clay, and a ble oil. This non-aqueous liquid trate forms
an aqueous dispersion when added to water and clings to a surface.
In many embodiments the non-aqueous liquid concentrate includes at least 20 wt% or at
least 25 wt% starch, at least 20 wt% or at least 25 wt% acrylic acid homopolymer salt, at
least 40 wt% ble oil, and up to 5 wt% clay. In many embodiments the non-aqueous
liquid concentrate includes from 20-30 wt% starch, 20-30 wt% acrylic acid homopolymer
salt, 40-60 wt% vegetable oil, and 1-5 wt% clay.
The non-aqueous liquid concentrate can have any useful viscosity. In many embodiments
the non-aqueous liquid concentrate is le or flowable, and can be shear thinning. In
many embodiments, viscosities (according to the test methods described herein) can range
from 5000 to 25000 cP or from 10000 to 25000 cP or from 5000 to 15000 cP.
The non-aqueous liquid concentrate includes a ble oil, a vegetable oil ester, or
combination thereof. Any vegetable oil or mixture of ble oils can be utilized in the
formulations described herein. Vegetable oil is a triglyceride that can be degraded
biologically. Some examples of vegetable oil are cottonseed oil; flaxseed oil; soybean oil;
safflower oil; sunflower oil; corn oil; canola oil; and peanut oil. The ble oil can be
any useful grade including food grade, partially hydrogenated, hydrogenated, or
ized grade, for example. Cottonseed oil appears to provide surprising gel formation
and fire protection results, as is illustrated in the examples below. In addition, vegetable
oil blends of cottonseed and soybean oil exhibited surprising reduced settling and
syneresis ed to single oil formulations.
In many embodiments the non-aqueous liquid concentrate and the resulting s
dilution does not include a pH modifier. pH modifiers include hydroxides, amines, and
other pH increasing elements. Many of these materials are corrosive by nature.
Carbomers (a series of acid polymers primarily made from c acid) can be found in
the industry which require specific pH l with strong alkalis such as hydroxides or
amines, in order to achieve a thickening effect in aqueous dispersions. Dispersions of the
carbomer into solution is more complex, requiring a multi-step neutralization or pH
adjustment process. Developing a non-aqueous liquid concentrate formulation that is non-
corrosive, and is shear thinning and/or thixotropic in a range of water qualities, was
desired.
Utilizing the c acid homopolymer salt eliminate the pH modification step or the
addition of corrosive or caustic materials to impart thickening. Selection and use of
l clays with select acrylic acid homopolymer salt provides the characteristics of both
pseudoplasticity and thixotropy at an optimal peak viscosity, and demonstrates a unique
synergy of these rheological characteristics, as illustrated in the Examples below.
Any useful starch can be used in the aqueous dispersions and precursors thereof.
Examples of starches and their modifications, include corn, wheat, potato, tapioca, barley,
oot, rice or any combination of starches. As an aqueous starch-containing
dispersion is heated, the starch will begin to swell at approximately 65 to 70 degrees
centigrade, turn into an amorphous, jelly-like mass at about 150 degrees centigrade, and
then as water is driven off, will decompose at approximately 230 degrees centigrade and
, giving off steam and CO2 as decomposition products. This behavior contributes to
the unique teristics of the aqueous dispersions in certain applications (e.g., fire
suppression). One particularly useful fied corn starch is known by the trade name
B20F, available from Grain Processing Corporation, Muscatine, Iowa. The non-aqueous
liquid concentrate compositions contain at least 15% starch or at least 20% starch, or at
least 25% starch.
The non-aqueous liquid concentrate and resulting aqueous dispersion can include an
acrylic acid homopolymer salt. In many ments, the acrylic acid lymer salt
is a polyacrylate homopolymer salt such as sodium rylate, for example. Sodium
polyacrylic acid homopolymers are effective plastic viscosity control agents or
thickening agents, and suspending agents at a neutral pH. In many embodiment, an acrylic
acid homopolymer salt does not require a pH modifier (e.g., sodium hydroxide, ect.,) to
build viscosity. Two useful acrylic acid homopolymer salts are known by the trade names
PNC 400™ and Neutragel DA™. They are neutralized homopolymers, also bed as
carboxyvinyl r sodium salts. PNC 400™ and Neutragel DA™ are commercially
available from 3V Sigma, Inc., Weehawken, NJ. The non-aqueous liquid concentrate can
contain at least 20 wt% acrylic acid homopolymer salt or from 20 to 30 wt% acrylic acid
homopolymer salt.
The non-aqueous liquid concentrate and resulting aqueous sion can include clay.
The clay can be included in any useful amount and can act as a suspending agent and/or
thickening agent. Useful l clays include water soluble clays derived from the
smectite family. These include Bentonite (montmorillonite), Hectorite, Saponite,
Sepiolite, Beidellite, Nontronite and Sauconite. The most common of these natural
smectite clays exhibit an octahedral structure. Hectorite appears as a ahedral
smectite, while montmorillonite can be referred to as a dioctahedral te. This refers
to the structure of the metal elements in the crystal lattice. When smectite clay platelets are
fully sed in water of low to moderate electrolyte content, they readily form an open,
three-dimensional colloidal dispersion of individual clay platelets. The individual platelets
are highly charged (positively on the edges and negatively on the faces) and stretch their
inter-layer distances when the inter-layer cations hydrate. This colloidal structure is also
commonly referred to as a 'house of cards' network that can thicken water and encourage
thixotropic behavior due to hysteresis observed and measured during recovery after
ng shear. These clay colloidal structures also impart the following characteristics to
aqueous systems: thickening, suspension, sag control, and stability. ite clays
provide higher viscosity, sag control, and lower iron content as compared to bentonite
clays. This is of particular importance when g with higher electrolyte-containing
aqueous systems. Iron can reduce the viscosity build of synthetic polymeric thickening
Commercially available hectorite clays are available under the trade designations
Bentone™ MA, and Bentone™ EW NA, available from Elementis lities Inc.,
town, NJ) for e. Commercially available sodium bentonite clays are
ble under the trade ations Volclay™ FD-181, available from American
d Company, (Hoffman Estates, IL) for example. Bentone™ MA and Bentone™
EW NA are natural hectorite clays that have been found to be unusually effective for
building viscosity in the aqueous dispersion in addition to imparting thixotropy. The non
aqueous liquid concentrate can contain from 1 to 5% clay.
In many embodiments, when diluted or dispersed into water or injected into a stream of
water, the non-aqueous liquid concentrate can make up from 0 .1 to 5 wt% or from 0.1 to 3
wt% or from 0.5 to 3 wt% or from 0.5 to 2 wt% of the aqueous dispersion. The aqueous
dispersion can have a l pH or a pH from 6.5 to 7.5 for example. This neutral pH
range is exhibited without utilizing a pH modifier such as strong alkalis such as
hydroxides or amines, in order to achieve a thickening effect in aqueous dispersions
needed to coat a substrate. The non-aqueous liquid concentrate and the aqueous
dispersion can be free of a pH modifier such as an alkali or amine.
In many embodiments, the ueous liquid concentrate has a viscosity less than 15000
cP or in a range from 8000 to 13000 with a Brookfield viscometer #6 spindle at 30 rpm
and a viscosity greater than 20000 cP or in a range from 20000 to 35000 with a #6 spindle
at 5 rpm. In many embodiments, the ueous liquid concentrate has a viscosity less
than 5000 cP or in a range from 4000 to 5000 with a Brookfield viscometer #4 spindle at
rpm and a viscosity r than 9000 cP or in a range from 9000 to 13000 with a #4
spindle at 5 rpm.
In many embodiments, a l%wt gel formed from the non-aqueous liquid concentrate has a
viscosity less than 8500 cP or in a range from 7000 to 8500 with a Brookfield viscometer
#5 spindle at 30 rpm and a viscosity greater than 35000 cP or in a range from 35000 to
40000 with a #5 spindle at 5 rpm.
The aqueous dispersion, described above, can be formed without a pH modifier such as
strong alkalis such as hydroxides or amines, for e. Excluding a pH modifier like
sodium hydroxide, for example, in the non-aqueous liquid concentrate and resulting
aqueous dispersion reduces the corrosivity of the non-aqueous liquid concentrate and
aqueous dispersion.
The size distribution has been found to affect the physical properties of the non-aqueous
liquid trate and ing aqueous dispersions. For example, illustrates a
non-aqueous liquid concentrate before and after size reduction via g or mixing. The
post-milled concentrate has a D99 of about 53 eters and the pre-milled trate
has a D99 of about 261 micrometers. D99 is the smallest particle diameter that is larger
than 99 vol% of particles in the distribution. is a graph of pre-milled and post-
milled non-aqueous concentrates particle size distribution curve for Example 13 below.
illustrates that the D99 of the pre-milled concentrate is about 261 micrometers and
the post-milled trate is about 54 micrometers.
Applicants have found that the non-aqueous liquid concentrate and resulting aqueous
dispersions possess surprising properties when the D99 is less than about 100
micrometers, or less than 50 micrometers, or greater than 25 micrometers, or greater than
micrometers. In many ments the concentrate or resulting aqueous dispersion
has a D99 in a range of about 25 to 100 micrometers or in a range from about 30 to 50
micrometers. D99 values less than this range produces concentrates that are too viscous to
easily inject or mix with water and trates with a D99 above this range do not gel as
y and do not possess other desirable physical attributes.
The non-aqueous liquid concentrate and resulting aqueous dispersions produced in the
Examples discussed herein exhibit "shear thinning" or "pseudoplastic" and "thixotropic"
character, which means the aqueous dispersion becomes thin when sheared or pumped
(pseudoplastic), and sag resistant (thixotropic), at rest, ng it to cling to substrates at
g angles. The non-aqueous liquid concentrate and resulting aqueous dispersion does
not separate or settle, maintaining a stable viscosity profile over an extended period of
time. Selection and use of natural clays with select acrylic acid homopolymer salts and
specific vegetable oils achieves the mentary teristics of both pseudoplasticity
and thixotropy at an optimal peak viscosity, demonstrating a unique synergy between the
selected materials, as rated in the Examples below.
Examples
Viscosity - Viscosities of the non-aqueous liquid concentrate and resulting aqueous
dispersions were ed using a Brookfield Viscometer, Model RVDVE. All samples
were measured at room temperature, with the viscometer set to a speed of 5 rpm, using
Spindle #6. For each sample, the spindle was immersed in the liquid concentrate or
aqueous dispersion and allowed to reach brium for 30 seconds prior to ng the
motor. Once a stable reading was displayed, the final viscosity was noted after an
additional 60 seconds, and recorded in centipoise (cP). Measurements are then repeated at
rpm.
Burn-Through Test - Each aqueous dispersion made from the Examples was subjected to
a burn test to determine a time value of when the sample aqueous dispersion loses
structural integrity and no longer protects the e from fire. A l"x6" pine wood
coupon that is uniformly coated using a Myer bar or similar apparatus with ¼ inch of
sample aqueous dispersion at a particular concentration, and placed 17 cm from the tip of
a e fueled flame apparatus measuring 1800 degrees F at the point of impingement
of the coated surface. The amount of time required to burn through the test material
coating and burn a 1 cm diameter scorch mark on the coupon is recorded. This test is
repeated four times.
Flame Test - Each non-aqueous liquid trate was subjected to a flame test to assess
the flammability of the material. A e torch was used for the evaluation
(Benzomatic TS4000 igniter/torch and Worthington Pro Grade Propane fuel - 14.1 oz size,
blue cylinder color). For each concentrate sample, a standard wood tongue depressor was
dipped into the concentrate to a depth of imately 2 inches and removed, held
vertically, and exposed to a continuous flame, with the flame held approximately 5 inches
from the al for 10 seconds. If the concentrate material exhibited a sustained flame
after removal of the flame source, results were noted as "flammable". If the concentrate
material showed no e flame immediately after removal of the flame source, results
were noted as "flame out."
Time to Gel - Each non-aqueous liquid concentrate was assessed for its ability to form a
viscous gel at a 1.0 % mix ratio in e osmosis water or deionized water. 5.0 grams of
concentrate material was measured into 495.0 g of water in a 1000 ml . The
samples were gelled using a Kitchen Aid™ immersion blender with a variable speed dial
set to the lowest speed (1). The blender was ed in the liquid. Two gel points were
noted: a) the time in s required for initial gel formation, bed as the visual
transition point between water and the first notable increase in viscosity resembling a gel,
and b) additional time in seconds required for a visually homogeneous and smooth gel.
Particle Size (D99) - Dispersions and mixture Examples below were analyzed for particle
size using a Horiba LA-950 laser scattering particle size analyzer. The analyzer
incorporates a solvent based flow system. Since samples were received as dispersions in
ble oil, they were analyzed using heptane as circulation bath medium. The
dispersions were pre-dispersed in heptane prior to analysis by introducing 0.5mL of the
sample to 15mL of heptane in a glass scintillation vial. The pre-dispersed sample was
mixed using a vortex. The analyzer was brought to heptane from water by rinsing twice
with IPA, twice with acetone, then filling with heptane. A refractive index of 1.53 was
used. This is similar to that of starch (related to the main ingredient in the dispersion). The
analyzer was d and d, and the pre-dispersed sample introduced to 70-85%
transmittance. The sample was ultrasonicated in the analyzer for 1 minute prior to
acquisition of the data. Mean diameter, D5, D10, D50, D90, and D99 data was obtained
from this analysis with the software associated with the Horiba LA-950 analyzer.
The materials utilized in these Examples are described below.
PNC 400™ is an acrylic acid homopolymer sodium salt (3V Sigma, Inc., Weehawken NJ)
Neutragel DA™ is a an c acid homopolymer sodium salt (3V Sigma, Inc.,
Weehawken NJ)
Bentone™ EW NA is a commercially available natural hectorite clay ntis
Specialities Inc., Highstown, NJ)
B20F, is a commercially available unmodified corn starch (Grain sing Corp.,
Muscatine IA)
Soybean Oil 100 is a commercially ble soybean oil (Columbus Vegetable Oils, Des
Plaines, IL) that is clear at zero degrees centigrade.
Roundy's Vegetable Oil is a commercially available soybean oil, (Roundy's
Supermarkets, Inc, Milwaukee, WI).
Soybean Oil 110 is a cially available winterized soybean oil (Columbus ble
Oils, Des Plaines, IL), partially hydrogenated and ized, high stability.
Cottonseed 300 is a commercially available cottonseed oil (Columbus Vegetable Oils, Des
Plaines, IL) non-winterized cottonseed oil.
Cottonseed 310 is a commercially available winterized cottonseed oil (Columbus
Vegetable Oils, Des Plaines, IL) that is clear at zero degrees centigrade.
, cottonseed, flax seed, canola, rice bran, safflower and peanut oils are all
commercially available from Soap Goods, Smyrna, GA.
Examples
The concentrate Examples of Table 1 and Table 2 were prepared from the following
ingredients using a FlackTek, Inc. SpeedMixer 150FVZ-K. This trate forms a gel
when 1% of the concentrate is mixed into DI water.
Table 1
A number of different vegetable oils were utilized in the formulation according to Table 1.
Table 2 describes the specific vegetable oil and the corresponding example identification.
Table 2
The es in Table 3 and Table 4 were prepared by using a bead mill mixer.
Table 3
A number of different vegetable oils (Example 13-15 in Table 4) were utilized in the
formulation illustrated in Table 3. Table 4 describes the ic vegetable oil and the
corresponding example identification.
Table 4
Results
Examples 1-12 were tested for concentrate viscosity and 1% aqueous dispersion (gel)
viscosity.
Table 5
Examples 1-12 were tested for time to gel and time to homogenous gel to form the 1%
aqueous dispersion as described above. Examples 1-12 were tested ing to the burn
test described above.
Table 6
All of the liquid concentrate examples showed no visible flame after removal of the flame
source during the flame test.
Examples 9-13 were tested as 1% gels in reverse osmosis (i.e., RO) water ing to the
burn test described above and the results below are an average of four tests for each
example.
Table 7
In view of the burn behavior of Example 12, Examples 12 and 13 were then tested further
at 1.5% in both RO (soft) water and municipal hard water (458 mg/1 CaCOs) measuring
ity and burn-through time as described above. Results below are the average of four
test replicates for each example.
Table 8
It is surprising that Example 12 es both a higher ity and burn-through time as
compared to e 13. Example 12 differs from Example 13 in that the e 12
vegetable oil is 50% cottonseed oil and 50% soybean oil and the Example 13 vegetable oil
is 100% soybean oil. is a particle distribution of a pre-milled and post-milled
Example 13 composition. e 13 was milled (e.g., mixed or homogenized) with a
bead mixer to reduce and homogenize the composition. illustrates that the D99 of
the pre-milled concentrate is about 261 micrometers and the post-milled concentrate is
about 54 micrometers.
The concentrate Examples of Table 9 and Table 10 were prepared from the following
ingredients using a FlackTek, Inc. SpeedMixer 150FVZ-K. This concentrate forms a gel
when 1% of the concentrate is mixed into DI water.
Table 9
A number of different vegetable oils were utilized in the formulation according to Table 9.
Table 10 describes the specific vegetable oil and the corresponding example identification.
Table 10
Concentrate samples were observed to be weakly flocculated to varying s. The
blends of n and cottonseed oils exhibited the greater degree of weak flocculation
("setting up"), with little to no syneresis. Being weakly flocculated is a positive attribute
with respect to ability to maintain the stability of the suspension (minimizing sis and
sedimentation/settling). Thus it is surprising that the blends of soybean and cottonseed
oils exhibited reduced syneresis and settling. Oils of same type (e.g., 100 % soybean or
100 % seed) exhibited greatest syneresis and did not "set up".
Viscosities of the non-aqueous liquid trate and resulting aqueous dispersions (gels)
were measured using a Brookfield Viscometer, Model RVDVE. All samples were
measured at room temperature, with the viscometer set to a speed of 5 rpm, using Spindle
#4 for the liquid concentrates and Spindle # 5 for the gels. For each sample, the spindle
was ed in the liquid concentrate or aqueous dispersion and allowed to reach
equilibrium for 30 seconds prior to starting the motor. Once a stable reading was
displayed, the final viscosity was noted after an additional 60 seconds, and recorded in
centipoise (cp). Measurements were then repeated after changing speed to 30 rpm and
recording viscosity after 60 seconds.
Table 11
The viscosities of the various gels made from the concentrates made with 50/50 soybean /
cottonseed oils showed the st viscosity ity (little comparative viscosity build)
over 24 hours, when compared to gels made from single-type oil concentrates. This is a
desirable attribute when storing or using prepared gels for a period of time.
1% gels in RO water and 1.4 % gels in ~ 230 mg/L CaC0 hardness water were prepared
and tested for burn-through. Tests were run tests in replicate and burn h times (in
seconds) recorded when an approx. 1cm diameter scorch mark is observed.
Table 12
Table 13
It is noteworthy that in the presence of hard water, or water with significant ionic strength,
burn-through data suggests that blending cottonseed oil with soybean oil, regardless of
grade, es greater consistency of the gel's cohesive and adhesive strength, resulting
in longer burn-through times for those gels, when ed to soybean oil only
concentrate-made gels. This enhancement is not as apparent when running the burnthrough
test in RO water at similar gel viscosities.
All of the liquid concentrate examples showed no visible flame after removal of the flame
source during the flame test.
Thus, ments of the NON-AQUEOUS LIQUID CONCENTRATE FOR
AQUEOUS DISPERSION are disclosed. The implementations described above and other
implementations are within the scope of the following claims. One skilled in the art will
iate that the present disclosure can be practiced with embodiments other than those
disclosed. The disclosed embodiments are presented for es of illustration and not
limitation, and the present invention is limited only by the claims that follow.
Claims (21)
1. A non-aqueous liquid concentrate comprising; starch; an acrylic acid homopolymer salt; vegetable oil; and clay; wherein, the non-aqueous liquid concentrate forms an aqueous dispersion when added to water and is capable of clinging to a e.
2. The ueous liquid concentrate according to claim 1 wherein the non-aqueous liquid concentrate has a particle size D99 value of 100 micrometers or less.
3. The non-aqueous liquid trate according to claim 1 wherein the non-aqueous liquid concentrate has a particle size D99 value in a range of 30 to 50 micrometers.
4. The non-aqueous liquid concentrate according to claims 1 to 3 wherein the vegetable oil comprises soybean oil.
5. The non-aqueous liquid concentrate according to claims 1 to 3 wherein the vegetable oil comprises cottonseed oil.
6. The non-aqueous liquid trate ing to claims 1 to 5 wherein the acrylic acid homopolymer salt comprises sodium polyacrylate.
7. The non-aqueous liquid concentrate according to claims 1 to 3 wherein the vegetable oil comprises seed oil and soybean oil.
8. The non-aqueous liquid trate according to claims 1 to 7 wherein the clay comprises a natural hectorite clay.
9. The non-aqueous liquid concentrate according to claim 1 comprising: at least 20 wt% starch; at least 20 wt% acrylic acid homopolymer salt; at least 40 wt% vegetable oil; and up to 5 wt% clay.
10. The non-aqueous liquid concentrate according to claims 1 to 9 wherein the non aqueous liquid concentrate has a le size D99 value of 50 micrometers or less.
11. The non-aqueous liquid concentrate ing to claims 1 to 10 comprising 40-60 wt% solids.
12. The non-aqueous liquid concentrate according to claims 1 to 11 comprising: 20-30 wt% starch; 20-30 wt% acrylic acid homopolymer salt; 1-5 wt% clay; and 40-60 wt% vegetable oil.
13. An aqueous sion composition comprising; water; and the ueous liquid concentrate according to claim 1-12; wherein the aqueous dispersion has a neutral pH, is shear thinning and thixotropic.
14. The aqueous dispersion according to claim 13 wherein the aqueous dispersion has a pH in a range from 6.5 to 7.5.
15. The aqueous dispersion according to claims 13 to 14 wherein the aqueous dispersion has solids concentration in a range from 0.5 to 3 wt%.
16. A method comprising; combining starch, acrylic acid homopolymer salt, clay and vegetable oil to form a ueous liquid concentrate according to claims 1-11.
17. The method according to claim 16 wherein the non-aqueous liquid concentrate has a viscosity of 15,000 or less using a Brookfield #6 e at 30 RPM and a viscosity of 20,000 or more using a Brookfield #6 spindle at 5 RPM.
18. The method according to claim 16 n the non-aqueous liquid concentrate is formed without the use of a pH modifier including a hydroxide or an amine.
19. A method comprising: forming the aqueous dispersion ing to claims 13-15; directing the aqueous dispersion onto a substrate and the aqueous dispersion clings to the substrate.
20. The method according to claim 19 wherein the aqueous dispersion is directed onto a substrate to suppress a fire.
21. The method ing to claim 19 wherein the forming step occurs by adding the non-aqueous liquid concentrate to a stream of water.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161543574P | 2011-10-05 | 2011-10-05 | |
US61/543,574 | 2011-10-05 | ||
US201261642110P | 2012-05-03 | 2012-05-03 | |
US61/642,110 | 2012-05-03 | ||
PCT/US2012/058857 WO2013055579A1 (en) | 2011-10-05 | 2012-10-05 | Non-aqueous liquid concentrate for aqueous dispersion |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ623683A NZ623683A (en) | 2015-04-24 |
NZ623683B2 true NZ623683B2 (en) | 2015-07-28 |
Family
ID=
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